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Definitions

• This invention relates to a precursor material, which can be decomposed to form semiconductors and metal oxides, or more generally, materials for electronic components.
• the precursors comprise metal complexes of hydroxamato ligands.
• the invention further relates to a preparation process for thin inorganic films comprising various metals (e.g. Cu/ln/Zn/Ga/Sn) and oxygen, selenium and/or sulfur.
• the thin films can be used in photovoltaic panels (solar cells), other semiconductor or electronic devices, and other applications using such films.
• the process uses molecular, metal containing precursor complexes with hydroxamato ligands. These can be combined in the process with chalcogenide sources or oxygen.
• various metal oxides and copper-based chalcopyrites of the l-lll-VI 2 type are prepared with high purity at low temperatures.
• Photovoltaic panels are normally made of either crystalline silicon or thin-film cells. Many currently available solar cells are configured as bulk materials that are subsequently cut into wafers and treated in a "top-down" method of synthesis, with silicon being the most prevalent bulk material. In an attempt to make cheaper panels, other materials are configured as thin-films (inorganic layers, organic dyes, and organic polymers) that are deposited on supporting substrates. l-lll-VI 2 -type copper-based semiconductors (chalcopyrite-type) like CulnSe 2
• CISS and CIGS have a direct bandgap that is tuneable by varying the In/Ga ratio or by varying the S/Se ratio to match the solar spectrum.
• CIGS is one of the most promising semiconductors capable to reaching 20.3 % power conversion efficiency in a thin film solar cell device, comparable to multicrystalline solar cells ⁇ Green et al., Prog. Photovoltaics, 2012, 20, 12).
• the Cu(Zn,Sn)(S,Se) 4 (CZTS) based solar cell is another promising low cost alternative that utilizes cheaper and earth abundant elements, with best reported solar cell efficiency of about 11.1 % (Todorov et al. Adv. Energy Mat, 2013, 3, 34-38).
• Solution processing of CIGS and CZTS offer a potential for cost reduction as compared to vacuum based techniques.
• the high efficiency CIGS devices are usually prepared using a complex vacuum based process i.e. 3-stage co- evaporation of metals under a constant source of selenium.
• the challenges include composition uniformity over large areas, precise control of flux/deposition rates to avoid intermediate phases and low material utilization (material also deposits on walls of the vacuum chamber).
• Solution based deposition methods can provide several
• the absorber layer can be solution processed using a particle based ink or precursor based ink or a mixture of both.
• a 12.0 % efficient device has been demonstrated by conversion of Cu(ln,Ga)S2 nanoparticle film to
• Nanosolar utilized binary metal selenides nanoparticles to achieve 15 % efficient device (1 r International Photovoltaic Science and Engineering Conference, Nanosolar Inc., Tokyo, Japan, 2007).
• IBM has demonstrated 15.2 % efficient CIGS device by processing a precursor ink made by dissolving metal selenides and sulfides in hydrazine (Todorov et al. Prog. Photovolt: Res. Appl., 2012, DOI: 10.1002/pip.1253, US 20090145482A1, US 20090121211, WO 1997023004).
• hydrazine is highly toxic and flammable that could limit the use of this method in a large scale manufacturing environment.
• Spray pyrolysis of metal salts like CuCI, InC , GaCI 3 with selenourea or thiourea and their derivatives is also shown to produce metal chalcogenide films.
• Fujdala et al. (US 2011/0030786 A1) reported synthesis of Cux(ln 1-y Gay)v((Si, z Se z )R)w polymeric precursor where elemental ratio and number of repeat units w could be varied and R represents an organic or inorganic ligand.
• Wang et al. dissolved metal oxides in butyldithiocarbamic acid, forming thermally degradable organometallic molecular precursor inks. Using these inks
• Cu(ln,Ga)(S,Se) 2 thin film solar cells exhibited an average efficiency up to 8.8% (Wang et al. Chem. Mater. 2012, 24, 3993).
• ZTO zinc tin oxide
• IZTO indium zinc tin oxide
• Zinc tin oxide can be obtained from anhydrous tin(ll) chloride or tin(ll) acetate and zinc acetate hexahydrate in the presence of bases, such as
• Indium zinc tin oxide is obtained from anhydrous indium chloride, zinc chloride and tin(ll) chloride in ethylene glycol by reaction with sodium hydroxide solution and subsequent calcination at 600°C (D.H. Lee et al. Journal of Materials Chemistry 2009, 19, 3135-3137).
• chalcogen according to this disclosure is limited to sulfur (S), selenium (Se) and to some degree tellurium (Te). Selenium (Se), sulfur (S) and combinations of S and Se are preferred chalcogens.
• a “chalcogen source” is any type of chalcogen or chalcogen containing compound(s).
• metal chalcogenide stands for metal sulfides, metal selenides or metal tellurides, and their combinations.
• metal stands for metals including main group metals, transition metals, lanthanides and germanium.
• a “binary” chalcogenide is one that is composed of a single metal and a chalcogenide, such as ln 2 S 3 or Cu 2 Se.
• a “ternary” chalcogenide means a material composed of two metals and chalcogenide, like CIS (CulnS 2 ) or
• CISS Culn(S,Se)2
• a "quaternary" chalcogenide analogously stands for a material consisting of three metals and chalcogenide, like CIGS.
• “Multinary” chalcogenides stand analogously for a material consisting of even more metals.
• l-lll-VI type semiconductor usually means a ternary chalcogenide mainly comprising metals from the groups 1 (aka IB) and 13 (aka IIIA), and chalcogenide (group 16).
• group 16 a "l-ll/IV-VI" type
• semiconductor means a quaternary chalcogenide mainly comprising metals from the groups 11 (aka IB) and 12 (aka MB), 14 (aka IVA) and chalcogenide
• CIGS copper indium gallium selenide/sulfide of varying elemental distribution, including the presence of other elements in a smaller amount.
• CZTS copper zinc tin selenide of varying elemental distribution. The compounds are often described alternatively by a variable molecular formula like
• the molecular formulae throughout this disclosure include such variations in the elemental distribution.
• sulfur in replacement of selenium, or vice versa, partly or fully can be present.
• other elements can be present, e.g. Ag replacing Cu, or Sn, Zn, Cd in CIGS, or In, Ge, Cd in CZTS, trace elements like Na, Sb, Te, As, etc.
• the ligands are derived from hydroxamic acids and N-substituted hydroxamic acids by deprotonation. The ligands can bind through this central structure as a bidentate chelate ligand, using the oxygen atoms as binding centers.
• metal complexes comprising hydroxamato ligands
• Metals, to which the hydroxamato ligands are bound include, but are not limited to, indium (In), gallium (Ga), zinc (Zn), tin (Sn), aluminium (Al), germanium (Ge), Yttrium (Y), Lutetium (Lu) and Europium (Eu), further iron (Fe), copper (Cu) and cadmium (Cd).
• precursors comprising one or more metal complexes and a chalcogen source are combined, at least one metal complex comprising at least one hydroxamato ligand, and
• the combined precursors are decomposed, preferably in an inert
• precursors comprising a metal complex comprising at least one hydroxamato ligand are decomposed, preferably in an oxygen containing environment, by heating or radiation with formation of the metal oxide.
• a further aspect of this invention is directed to a precursor comprising at least one metal complex with a hydroxamato ligand, and that precursor can be decomposed to form a semiconductor, electronic component or a metal oxide.
• Still another aspect of the invention is directed to a precursor composition comprising at least one metal complex with a hydroxamato ligand and a chalcogen source and that precursor composition can be decomposed to form a semiconductor.
• R 1 is selected from Ci to C15 alkyl, phenyl or benzyl, preferably alkyl, more preferably Ci to C 6 alkyl, and most preferably methyl, ethyl, iso-propyl or tert-butyl.
• R 2 is selected from H, Ci to C 6 alkyls, preferably H, CH 3 or CH 2 CH 3 , and more preferably H.
• the hydroxamato ligand is a chelate ligand with one negative charge. As a chelate ligand it bonds to the metal via the two oxygen atoms. According to this invention the hydroxamate ligand is not to be confused with the neutral hydroxamic acids of formula LH, which also have some ligand properties.
• the preferred mode for decomposition of the precursors is by heating, including baking, micro-waving, UV radiation and thermal radiation.
• chalcogen according to this invention is limited to sulfur (S), selenium (Se) and to some degree tellurium (Te).
• Selenium (Se), sulfur (S) and combinations of S and Se are preferred chalcogens, whereas
• One, preferably two or all of the metal precursors of a precursor composition according to the invention comprise one or more hydroxamato ligand.
• one or more of the metals can be employed as known precursors, including e.g. acetylacetonates, acetates, oximates and other salts.
• the metal complexes are preferably metal hydroxamato complexes comprising the maximum number of hydroxamato ligands depending from their valence.
• a preferred zinc hydroxamate has e.g. the structure Zn(L)2 with two hydroxamate ligands of the formula (L) described above.
• a complex of formula [Zn(L)(LH)] + would be less preferable, since it requires an additional anion.
• the complexes have two, three or more hydroxamato ligands.
• Metals which are preferably used with hydroxamato ligands, include aluminium, gallium, cadmium, copper, germanium, neodymium, ruthenium, magnesium, hafnium, indium, silver, tin, zirconium and zinc, preferably copper, indium, gallium, indium, zinc, aluminium, germanium, or tin.
• the semiconductors containing chalcogenide and which are formed in the process according to the invention are preferably of the I-III-VI2 or I-II/IV-VI2 type.
• the l-lll-VI 2 type semiconductors one or more (+111) valency metals are used, preferably selected from In and Ga, more preferably In and In combined with Ga.
• the monovalent metal is preferably copper.
• the trivalent metals are preferably indium or gallium. Mixtures of these metals can be employed for tuning the band-gap of the semiconductor.
• the tervalent metal can be exchanged partly or completely against a mixture of divalent and tetravalent metals (l-ll/IV-VI 2 -type semiconductor, e.g.
• Divalent metals are preferably cadmium or zinc, tetravalent metals are preferably germanium or tin.
• the metal oxides formed in the process according to the invention are preferably copper oxide, indium oxide, gallium oxide, indium oxide, zinc oxide, aluminium oxide, germanium oxide, tin oxide and mixed metal oxides such as indium tin oxide, indium zinc oxide, gallium zinc oxide, indium gallium zinc oxide, aluminium zinc oxide etc. These metal oxides have various useful applications in electronics as conductors or semiconductors.
• the precursors are preferably combined in a liquid phase, preferably a solvent providing good solubility of the components, and thus complete mixing of the metals with the optional chalcogen source is assured.
• the liquid phase preferably comprises an organic solvent or a mixture of two or more organic solvents. Usually the solvent evaporates quickly when the mixture is applied to a substrate and heated to at least above the boiling point of the solvents.
• the precursor composition is preferably deposited on a substrate prior to decomposition, preferably by dip coating, spray coating, rod coating, spin coating, slit coating, drop casting, doctor blading, ink-jet printing or
• the semiconductor or metal oxide is made by spray pyrolysis.
• the coating step is preferably repeated, intermitted or not by decomposition and /or heating of the material.
• the semiconductor materials consist of almost pure selenide/sulfide phases of the metals.
• a source of chalcogen in the process usually a pure chalcogenide phase is formed.
• the level of impurities of the elements C/N/CI is considerable lower than observed with methods according to prior art.
• the precursors are very stable in solution even at neutral conditions. This is a benefit over solutions made from metal chlorides and thiourea/selenourea which cause flocculation and have a considerable content of halogen. Alternatively an amount of acid or ethanolamine has to be added to stabilize those solutions.
• all of the current process steps can be performed under ambient pressure, which is a great economic benefit over previous vacuum deposition methods.
• the precursor composition consists of a liquid phase containing the precursor materials.
• the liquid phase can easily be processed by transferring it to surfaces to be covered with semiconducting material by spraying, dropping, dipping, printing etc.
• the liquid phase may preferably comprise organic solvents and solvent mixtures, more preferably solvents in which the precursors are soluble, mostly preferred polar-aprotic solvents like dimethylformamide (DMF), dimethyl sulfoxide (DMSO), etc and protic solvents like methanol, ethanol, 2-methoxyethanol, isopropanol etc.
• DMF dimethylformamide
• DMSO dimethyl sulfoxide
• the thermal decomposition temperature of the precursor system according to the invention is as low as 150 °C and the end product after decomposition contains very low amounts of impurity elements like C or N ( ⁇ 1 %).
• the semiconductor layer typically has a thickness of 5 nm to 5 ⁇ , preferably 30 nm to 2 ⁇ .
• the layer thickness is dependent on the coating technique used in each case and the parameters thereof. In the case of spin coating, these are, for example, the speed and duration of rotation. In the case of spraying, the thickness can be increased with spraying time. In the case of rod coating and doctor blading the thickness can be increased by repeated deposition steps.
• the substrate can be either a rigid
• substrate such as glass, ceramic, metal or a plastic substrate, or a flexible substrate, in particular plastic film or metal foil.
• substrate such as glass, ceramic, metal or a plastic substrate, or a flexible substrate, in particular plastic film or metal foil.
• substrate coated with plastic film or metal foil preference is given to the use of a substrate coated with plastic film or metal foil.
• molybdenum which is very effective for the performance of solar cells.
• the present invention furthermore relates to a process for the production of an electronic structure, preferably a device comprising a layered
• Steps a) and b) can be performed concurrently by e.g. spraying on a hot substrate (spray pyrolysis). Repeating of step a) can be intermitted by one or more of steps b), which is preferred.
• the process produces semiconducting or electronic components and optionally the connections of the components in a electronic structure.
• the electronic structure can be part of a photovoltaic device, wherein the absorber layer comprises the produced semiconductor.
• Certain metal oxides made easily accessible by the current invention are useful as transparent conductors or photoconductors.
• photovoltaic device is fabricated by depositing a precursor composition according to the invention, which is preferably solvent-based, onto a substrate and thermally decomposing the one or more precursors to obtain the semiconductor layer.
• a precursor composition according to the invention which is preferably solvent-based
• thermally decomposing the one or more precursors to obtain the semiconductor layer.
• a copper-selenium precursor and an indium precursor are co-deposited and heated in an inert or air environment afterwards in order to obtain a CIS layer.
• the precursor composition comprises relative amounts of the metal precursors which are equivalent to the stoichiometry of the desired semiconductor.
• the precursor composition comprises relative amounts of the metal precursors which are equivalent to the stoichiometry of the desired semiconductor.
• equimolar amounts of copper and indium precursor would be employed.
• the copper and indium precursor ratios can also be adjusted to make either slightly copper poor or copper rich CIS layers. Slightly copper poor CIS compositions have been shown in literature to have better photovoltaic performance (S. Siebentritt et ai, Solar Energy Materials & Solar Cells 2013, 119, 18-25).
• an additional compound comprising S, Se and/or Te and not comprising a metal is added into the process. It may be added at step a) by adding the compound to the combined precursors (the precursor composition) or during/after
• This optional source of S/Se/Te which adds additional chalcogen, is preferably selected from organic compounds comprising selenium or sulphur or elemental selenium, sulphur or tellurium, more preferably from selenourea/thiourea or their derivatives by exchanging hydrogen with other organic groups, thioacetamide, or elemental S/Se/Te dissolved or suspended as a powder in amines (like hydrazine,
• chalcogens Sulfur and selenium are preferred chalcogens in this specification.
• the precursor composition for chalcogenide formation comprises at least an amount of the chalcogen components relative to the amount of metal which is equivalent to the stoichiometry of the desired semiconductor or more.
• an excess amount of the chalcogen can be used, because some of the selenium or sulfur may be lost due to the chalcogen volatility during annealing and decomposing the precursor composition.
• the amount of chalcogen is preferably 100 % (stoichiometric, 0% excess) to 400 % (300 % excess) relative to the theoretical metal content, more preferably 10 - 50 % excess.
• stoichiometric amounts of sulfur and additional selenium is included in the precursor comprising the first metal.
• the precursor composition can be deposited on a "hot" substrate to
• Another method to produce the semiconductor or oxide material or the absorber layer is to deposit the precursor solution onto a substrate held at a temperature below the temperature of decomposition, typically at room temperature. This step is followed by annealing the films preferably in inert environment at the decomposition temperature of the precursors to convert the precursor films into a semiconductor layer, e.g. a CIS layer.
• intermediate step can be the evaporation of the liquid carrier. This method provides more time to evenly distribute the precursor composition in the required form or thickness onto a substrate.
• the precursor composition is spray dried into hot inert gas providing a fine powder or grains of the semiconductor.
• the thermal conversion of the metal complex precursor into the functional semiconductor layer is carried out at a temperature > 150°C, preferably ⁇ 200 °C and more preferably > 300 °C.
• the temperature is preferably between 150 and 400°C. Oxides made by one of the inventive processes may be
• the first decomposition step can be followed by further annealing steps to improve the electronic properties and
• crystallinity and/or grain size of the semiconductor preferably the layer of semiconductor (more preferably CIS or CIGS layer).
• the grain size of the semiconductor film can be increased by increasing the annealing
• the process for the manufacture of a photovoltaic device according to the invention is free of any additional selenization and/or sulfurization step at temperatures above 250 °C. This way the temperatures in a process can be kept at 200 °C or lower.
• the inventive process according to the invention includes as a further step a selenization and/or sulfurization step and/or an annealing step after the decomposition of the precursors.
• the amount of chalcogen in the annealed films can be controlled by the initial chalcogen content in the precursor solution, by the amount and type of chalcogen present in the vapor phase and by the annealing/decomposition temperature and time.
• the conversion of the metal complex precursor or the precursor composition into the functional semiconductor layer is carried out in a further preferred embodiment by irradiation, preferably electromagnetic irradiation, including microwaves, IR, and UV, with preference to UV light at wavelengths ⁇ 400 nm.
• the wavelength is preferably between 150 and 380 nm.
• the advantage of UV irradiation is that the layers produced thereby have lower surface roughness.
• the electronic component is provided with contacts to the semiconductor or metal oxide and completed in a conventional manner.
• a transparent top electrode made from e.g. ZnO or indium-tin oxide and a metal grid is provided.
• Conventional means may be employed to optimize the photovoltaic device performance.
• Selenization/sulfurization (see above), treatment with aqueous cyanide to remove traces of copper selenide or copper sulfide, a
• thioacetamide/lnCl 3 wash for band gap optimization and application of various contact layers may be employed to the
• the present invention furthermore relates to the use of the metal complex or precursor composition according to the invention for the production of one or more functional layers, preferably the absorber layer, in a photovoltaic device.
• the precursors or complexes are formed at room temperature by reaction of a hydroxamic acid with at least one metal salt, such as, for example, nitrates, chlorides, oxichlorides, etc. in the presence of a base, such as, for example, ammonia, tetraethylammonium hydrogencarbonate or sodium
• hydroxamic acids are lower alkyl derivatives (Ci - CQ), wherein the alkyl group can be branched or linear.
• Hydroxamic acids can be prepared in a known manner from the reaction of carbonic acid chlorides with hydroxylamine or N-alkylhydroxylamines or their respective salts.
• GaCI 3 (1.439 g, 8.17 mmol) was dissolved in 20 ml of water, and 17 ml of a 1 molar solution of ammonia was added under stirring.
• pivalohydroxamic acid (2.9 g, 24.8 mmol) in ethanol (60 ml) was added to this mixture, followed by another 7.8 ml of 1 molar ammonia solution. All volatiles were removed under vacuum after stirring the mixture for 20 h at room temperature, and the remainder was extracted with a mixture of 400 ml of CH 2 CI 2 and 100ml of ethanol. The extract was cleared from precipitated NH 4 CI by-product by filtration and evaporated to dryness again. The as- obtained white powder was dissolved in 30 ml of hot ethanol, and 100 ml of water was added. The resulting mixture was concentrated in vacuo on a rotary evaporator until the onset of precipitation.
• Aluminium isopropoxide (1.021 g, 5 mmol) was added under stirring to a hot solution of isobutyrohydroxamic acid (1.547 g, 15 mmol) in dry ethanol (30 ml), and the mixture was heated under reflux for 15min.
• the product precipitated partially as a fine white powder already during the dissolution of the aluminium isopropoxide. More product formed upon cooling, which was collected by filtration after stirring at ambient temperature for 5 h. Washing with 5 ml of ethanol and 2 ⁇ 10 ml of ether afforded 1.545 g (4.64 mmol, 92 %) of white powder after drying in vacuo. Elemental analysis calc. (found) for
• Solid stannous methoxide (1 g, 5.52 mmol) was added in portions to a solution of isobutyrohydroxamic acid (1.14 g, 1 1 .1 mmol) in dry ethanol (40 ml), and the mixture was stirred at 40°C until dissolution was completed.
• White needles formed within 24 h at -20°C after concentration to 20 ml in vacuo and dilution with an equal volume of ether. Filtration, washing with 2 ⁇ 10 ml of ether and drying in vacuo afforded 1 .064 g (3.30 mmol, 60 %).
• Triethylamine (66 ml, 47.92 g, 474 mmol) was added dropwise to a stirred solution of N-methylhydroxylamine hydrochloride (15.87 g, 190 mmol) in methanol (100 ml) at 0-5°C. After stirring for 30 min, acetyl chloride (17.27 g, 15.6 ml, 220 mmol) was slowly added dropwise, and the resulting slurry was allowed to warm to ambient temperature under stirring. 500 ml of ether was added, and the precipitated triethylammonium chloride was removed by filtration and washed with ether (3 x 100 ml).
• TGA Thermogravimetric analysis
• the extrusion of an organoisocyanate from a hydroxamato ligand in course of the proposed decomposition process leaves a hydroxo ligand on the metal center.
• the resulting metal hydroxides will then convert under subsequent condensation into the finally obtained metal oxide phase.
• the proposed Lossen rearrangement mechanism may also account for the fact that pure metal oxide phases are isolated even if the decomposition is carried out in an inert atmosphere.
• the ceramic yields obtained in almost all studied degradation experiments under helium atmosphere approach the expected values for the respective metal oxide phases which were detected by X-ray diffractometry if the annealing was carried out in air (vide infra).
• the deviation from the expected ceramic yield that was obtained in the degradation of both the pivalo- and isobutyrohydroxamato complexes of Ga(lll) does not indicate the Lossen rearrangement mechanism applies here.
• the ceramic yield of the Ga and In derivatives at 600°C falls below the respective theoretic value distinctly, thereby indicating major mass losses due to sublimation of intact molecules, which in turn points to an increased volatility and thermal robustness of the respective precursor complexes.
• This deviating behavior of the N-methyl-acetohydroxamato metal complexes may be ascribed to the fact that the presence of the methyl substituent on the N atom in this ligand will prevent the necessary
• a stock solution of 5 wt % precursor complex concentration with In/Sn ratio of 9 : 1 was prepared by dissolving tris(0,0-isobutyrohydroxamato)indium (1 17 mg, 0.278 mmol) and bis(0,0-isobutyrohydroxamato)tin (10 mg, 0.031 mmol) in 2.64 ml 2-methoxyethanol under moderate warming.
• the solution was filtered through a 0.2 pm PTFE syringe filter after cooling to ambient temperature directly before use.
• Silicon wafer and alkaline-free glass substrates (15 x 15 mm), as well as quartz substrates (10 ⁇ 10 mm), were cleaned by subsequent washing with acetone and isopropanol in an ultrasonicator, followed by air-plasma treatment for 1 min.
• ITO films were prepared by spin-coating of the stock solution onto the respective substrate (1000 rpm for 6 s, 2500 rpm for 20 s), followed by thermal decomposition on a hotplate in ambient air for 5 min at 400 or 450°C, respectively, and subsequent cooling in an argon stream for 10 s.
• Example 20 A photovoltaic CIGS device made from spray coating an ink based on hydroxamato precursors.
• a CIGS precursor ink was made by dissolving Tris(N-methylaceto- hydroxamato)gallium (CH 3 CON(CH 3 )0) 3 Ga (0.375 mmol), Tris(N- methylacetohydroxamato)indium (CH 3 CON(CH 3 )0)3ln (0.7 mmol),
• Diaquabis(2-hydroxyiminopropionato)copper (0.95 mmol) (copper precursor prepared similar to literature M. Aymaretto, Gazzetta Chimica Italiana, 1927, 57, 648; Kirillova et al., Acta Cryst. 2007, E63, m1670) and selenourea (4 mmol) in 5 ml DMSO. A small amount of ethanolamine (0.05 ml) was added to the above solution to prevent the reaction between copper and selenium precursors. A greenish brown solution without any residues was obtained showing complete dissolution of the precursors.
• the precursor ink was sprayed over a 1" ⁇ 1 " molybdenum coated glass substrate kept at 350 °C in a nitrogen environment with oxygen and moisture levels below 5 ppm.
• An about 2.5 ⁇ thick smooth and crack free CIGS film was prepared by spraying.
• the CIGS film was transferred to a graphite box with a lid (not air tight) with a few selenium shots.
• the graphite box assembly was inserted in an argon filled quartz tube and heated in a tube furnace.
• the tube furnace was maintained at 550 °C and selenization is performed for 50 min under vacuum.
• selenium pellets create selenium vapor over the substrate inside the enclosed graphite box and help to promote grain growth and higher crystallinity in the films.
• Figure 5 shows the x-ray diffraction pattern of sprayed and selenized films.
• Figure 5 part (a) shows a broad peak (112) corresponding to nanoparticulate grain size of sprayed Culn x Ga ( i -X )Se 2 film as well as peak from molybdenum substrate.
• the average grain size of sprayed film was calculated to be 8 nm by Debye-Scherrer formula.
• the (112) peak width also decreases significantly due to grain growth. Further smaller peaks such as (101), (211 ) appear showing chalcopyrite phase and higher crystallinity.
• molybdenum selenide (MoSe 2 ) peaks can also be observed in Figure 5 part (b) due to reaction of molybdenum with selenium vapor during selenization.
• the peak intensity for Mo is smaller after selenization showing that significant amount of the molybdenum is converted to molybdenum selenide.
• Figure 6 shows the scanning electron microscopy (SEM) image of the cross- section of the selenized CIGS layer on molybdenum substrate.
• Majority of the grains are large columnar type > 1 ⁇ in size except for a thin layer in the middle of the film that shows nano size grains.
• SEM scanning electron microscopy
• EDS Energy Dispersive Spectrometry
• Copper poor CIGS films are desirable to achieve high quality photovoltaic- grade semiconductor.
• CdS layer ⁇ 50 nm was deposited from a solution method described elsewhere ⁇ M.A. Contreras et al. Thin Solid Films 2002, 403-404, 204-211). ZnO (50 nm) and ITO (300 nm) thin films were deposited sequentially by RF sputtering. Next a 300 nm thick Ag current collection grid was deposited by DC sputtering.
• Figure 7 shows the IV characteristics under dark and AM1.5 light condition for the solar cell comprising the CIGS thin film made from hydroxamato based precursor ink.
• the efficiency of the solar cells can be improved further by optimization of annealing time/temperature, controlling Se/S vapor pressure during sulfurization or selenization, introducing gallium gradients in the CIGS film, optimization of Na and other dopants, optimization of other layers of the device.
• Fig. 1 TGA traces of a: isobutyrohydroxamato (iBuH) metal complexes; b: pivalohydroxamato (PvH) metal complexes; c: N-methyl-acetohydroxamato (MeAcH) metal complexes. All TG experiments were performed under helium atmosphere at a heating rate of 10°C min "1 .
• Fig. 2 X-ray powder diffractograms of pivalohydroxamato metal complexes after annealing at various temperatures.
• Fig. 3 X-ray powder diffractograms of isobutyrohydroxamato metal complexes after annealing at various temperatures.
• the reference spectrum (ICSD) is reproduced on the baseline.
• AI(lll)iBuH the baseline shows alpha and gamma-A ⁇ Os, and the graphs 3 and 4 are in good agreement with the gamma-Al 2 O 3 reference spectrum.
• Fig. 4 X-Ray diffractograms of ten-layer ITO thin films on alkaline-free glass supports annealed at a: 400°C; and b: 450°C, measured in reflection mode.
• Fig. 5 The graphs shows X-ray diffraction patterns (intensity plotted against diffraction angle 2 theta) of films according to the invention for a) CIGS film sprayed using hydroxamato precursor based ink and b) CIGS film after selenization of sprayed CIGS film by replacement of S by Se,
• Fig. 6 This figure shows the scanning electron microscopy (SEM) image of the cross-section of the selenized CIGS layer on molybdenum substrate.
• SEM scanning electron microscopy
• Fig. 7 The graph shows the photovoltaic device response under dark and AM .5 light condition of a CIGS solar cell described in device Example 20.

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